Correction of ground-water chemistry and carbon isotopic composition for effects of CO₂ outgassing     

F.J. Pearson  Donald W. Fisher  L.N. Plummer 《Geochimica et cosmochimica acta》1978,42(12):1799-1807

Direct measurements on water samples from several CO₂-charged warm springs are significantly higher than values calculated from field pH and alkalinity (and other constituents). In addition, calcite saturation indices calculated from field pH and solution composition indicated supersaturation in samples which, on the basis of hydrogeologic concepts, should be near saturation or undersaturated. We attribute these discrepancies to uncertainties in field pH, resulting from CO₂ outgassing during pH measurement. Because samples for direct measurement can be taken with minimal disturbance to the water chemistry, we have used the measured to back calculate an estimate of the field pH and the carbon isotopic composition of the water before outgassing. By reconstructing water chemistry in this way, we find generally consistent grouping of $\text{δ}{}^{13}\text{C}$, pH, and degree of calcite saturation in samples taken from the same source at different times, an observation which we expect based on our understanding of the hydrogeology and geochemistry of the ground-water systems. This suggests that for very careful geochemical work, particularly on ground-waters much above ambient temperature, measurements may provide more information on the system and a better estimate of its state of saturation with respect to carbonate minerals than can field measurements of pH.  相似文献   

Arsenic and antimony in geothermal waters of Yellowstone National Park,Wyoming, USA     

Robert E. Stauffer  John M. Thompson 《Geochimica et cosmochimica acta》1984,48(12):2547-2561

A total of 268 thermal spring samples were analyzed for total soluble As using reduced molybdenum-blue; 27 of these samples were also analyzed for total Sb using flame atomic absorption spectrometry. At Yellowstone the $\text{Cl}\text{As}$ atomic ratio is nearly constant among neutral-alkaline springs with Cl > 100 mg L^?1, and within restricted geographic areas, indicating no differential effects of adiabatic vs. conductive cooling on arsenic. The $\text{Cl}\text{As}$ ratio increases with silica and decreases with decreasing $\text{Cl}\text{ΣCO}{}_3$; the latter relationship is best exemplified for springs along the extensively sampled SE-NW trend within the Lone Star-Upper-Midway Basin region. The relationship between $\text{Cl}\text{As}$ and $\text{Cl}\text{ΣCO}{}_3$ at Yellowstone suggests a possible rock leaching rather than magmatic origin for much of the Park's total As flux. Condensed vapor springs are low in both As and Cl. Very high $\text{Cl}\text{As}$ ratios ( > 1000) are associated exclusively with highly diluted (Cl < 100 mg L^?1) mixed springs in the Norris and Shoshone Basins and in the Upper White Creek and Firehole Lake areas of Lower Basin. The high ratios are associated with acidity and/or oxygen and iron; they indicate precipitation of As following massive dilution of the Asbearing high-Cl parent water.Yellowstone Sb ranged from 0.009 at Mammoth to 0.166 mg L^?1 at Joseph's Coat Spring. Within basins, the $\text{Cl}\text{Sb}$ ratio increases as the $\text{Cl}\text{ΣCO}{}_3$ ratio decreases, in marked contrast to As. Mixed springs also have elevated $\text{Cl}\text{Sb}$ ratios. White (1967) and Weissberg (1969) previously reported stibnite (Sb₂S₃), but not orpiment (As₂S₃), precipitating in the near surface zone of alkaline geothermal systems.  相似文献   

Evaluation of deep temperatures of hydrothermal systems by a new gas geothermometer     

Franco D&#x;Amore  Costanzo Panichi 《Geochimica et cosmochimica acta》1980,44(3):549-556

The chemical composition of gas mixtures emerging in thermal areas can be used to evaluate the deep thermal temperatures. Chemical analyses of the gas compositions for 34 thermal systems were considered and an empirical relationship developed between the relative concentrations of H₂S, H₂, CH₄ and CO₂ and the reservoir temperature. The evaluated temperatures can be expressed by: $\text{t°C =}\text{24775}\text{α + β + 36.05}\text{?273}$ where $\text{α = 2 log}\text{CH}{}_4\text{CO}{}_2\text{?log}\text{H}{}_2\text{CO}{}_2\text{?3 log}\text{H}{}_2\text{S}\text{CO}{}_2$ (concentrations in % by volume) and β = 7 logP_co2  相似文献   

Sodium and potassium coprecipitation in aragonite     

Art F White 《Geochimica et cosmochimica acta》1977,41(5):613-625

The coprecipitation of Na and K was experimentally investigated in aragonite. The distribution functions were determined at pH 6.8 and 8.8 over aqueous Na and K concentrations of between 5 × 10^?4and 2.0 M and temperatures of between 25 and 75°C.The mole fractions of Na and K in aragonite are related to the aqueous ratios of Na and Ca by a function of the form where C₀ and C₁ are constants at a given temperature. This equation was derived by a statistical model assuming a heterogeneous energy distribution for the sites of incorporation. The independence of the coprecipitation process from aqueous anion activities suggests that carbonate is the only anionic species in the solid solution.  相似文献   

Intrinsic oxygen fugacity measurements: techniques and results for spinels from upper mantle peridotites and megacryst assemblages     

Richard J. Arculus  John W. Delano 《Geochimica et cosmochimica acta》1981,45(6):899-913

A new technique for the determination of intrinsic oxygen fugacities () of single and polyphase geological samples with solid ZrO₂, oxygen-specific electrolytes is described. Essentially the procedure involves isolating the emf signal from the sample from that unavoidably imposed by the residual atmosphere inside the sample-bearing sensor. By varying the of the residual atmosphere, it is possible to determine a ‘plateau’ value of constant recorded from the sensor which represents a reversed intrinsic measurement for the sample alone, and where the extent of the plateau reflects the innate buffering capability of the sample. A measure of the precision and accuracy of the data obtained is the fact that identical values are obtained whether on a heating or cooling cycle of the sample + compatible atmosphere system.These techniques have been applied to measurements of the intrinsic of spinels from peridotites and megacryst assemblages from Australia, West Germany and the U.S.A. Oxidation states range from ～- 0.25 log₁₀ units more oxidized to 1 log₁₀ unit more reduced than the iron-wüstite (IW) buffer. The overall reduced nature of the spinels and the range of 's obtained are striking features of the data. One implication of the results is that the majority of mantle-derived magmas are initially highly reduced, and the relatively oxidized values observed at surface (～- 4–5 log₁₀ orders more oxidized than IW) reflect late-stage alteration, perhaps by H₂ loss (Sato, 1978).  相似文献   

Distribution coefficients of Eu and Sr for plagioclase-liquid and clinopyroxene-liquid equilibria in oceanic ridge basalt: an experimental study     

Richard J. Williams 《Geochimica et cosmochimica acta》1974,38(9):1415-1433

The distribution coefficients of Eu and Sr for plagioclase-liquid and clinopyroxene-liquid pairs as a function of temperature and oxygen fugacity were experimentally investigated using an oceanic ridge basalt enriched with Eu and Sr as the starting material. Experiments were conducted between 1190° and 1140°C over a range of oxygen fugacities between 10^?8 and 10^?14 atm.The molar distribution coefficients are given by the equations: log^PL_Sr = 7320/T ? 4.62logK^CPX_Sr = 18020/T ? 13.10. Similarly, the weight fraction distribution coefficients are given by the equations: logD^PL_Sr = 6570/T ? 4.30logD^CPX_Sr = 18434/T ? 13.62.Although the mole fraction distribution coefficients have a smaller dependence on bulk composition than do the weight fraction distribution coefficients, they are not independent of bulk composition, thereby restricting the application of these experimental results to rocks similar to oceanic ridge basalts in bulk composition.Because the Sr distribution coefficients are independent of oxygen fugacity, they may be used as geothermometers. If the temperature can be determined independently — for example, with the Sr distribution coefficients, the Eu distribution coefficients may be used as oxygen geobarometers. Throughout the range of oxygen fugacities ascribed to terrestrial and lunar basalts, plagioclase concentrates Eu but clinopyroxene rejects Eu.  相似文献   

Methane solubilities in multisalt solutions     

Patricia A. Byrne  Ronald K. Stoessell 《Geochimica et cosmochimica acta》1982,46(11):2395-2397

Solubilities of methane in multisalt solutions at 550 psia and 25°C can be predicted from single-salt salting coefficients. The ionic strength contribution of the ith salt, I_i, is multiplied by its molal salting coefficient, k_mi, in the following summation over all salts: where m_o and m_s are molal methane solubilities in distilled water and the salt solution, respectively, at the T, P and methane fugacity of interest.This equation predicts methane solubility in multisalt brines containing Na⁺, K⁺, Mg⁺², Ca⁺², Cl^?, SO₄^?2 and CO₃^?2 ions. k_mi values reported by Stoessell and Byrne (1982b) can be used in solubility predictions in brines at earth surface conditions. Prediction in reservoir brines would require determination of k_mi, for the different salts at reservoir temperatures and pressures.  相似文献   

Uptake of fluoride by aragonite     

M. Ichikuni 《Chemical Geology》1979,27(3):207-214

The uptake of F by aragonite is attributed to the ion-exchange process, in which one CO₃^2? ion in the structure is replaced by two F^? ions. Under the equilibrium condition at 15° C and 1 atm., the partition of F between aragonite and aqueous solution is described by: were [F] denotes the F content of aragonite in mol/g, and a_F and a_Ca are the aqueous activities of F^? and Ca²⁺, respectively. The equation was successfully applied to estimating the F content of marine aragonite.  相似文献   

Estimation of the dielectric constant of H2O from experimental solubilities of quartz,and calculation of the thermodynamic properties of aqueous species to 900°C at 2 kb     

William F. McKenzie  Harold C. Helgeson 《Geochimica et cosmochimica acta》1984,48(11):2167-2177

Experimental quartz solubilities in H₂O (Anderson and Burnham, 1965, 1967) were used together with equations of state for quartz and aqueous species (Helgesonet al., 1978; Walther and Helgeson, 1977) to calculate the dielectric constant of H₂O () at pressures and temperatures greater than those for which experimental measurements (Heger, 1969; Lukashovet al., 1975) are available ($\text{0.001 ? P ? 5}\text{kb}$ and $\text{0 ? T ? 600°C}$). Estimates of computed in this way for 2 kb (which are the most reliable) range from 9.6 at 600°C to 5.6 at 800°C. These values are 0.5 and 0.8 units greater, respectively, than corresponding values estimated by Quist and Marshall (1965), but they differ by <0.3 units from extrapolated values computed from Pitzer's (1983) adaptation of the Kirkwood (1939) equation. The estimates of generated from quartz solubilities at 2 kb were fit with a power function of temperature, which was then used together with equations and data given by Helgeson and Kirkham (1974a,b, 1976) Helgesonet al. (1981), and Helgeson (1982b, 1984) to calculate Born functions, Debye Hückel parameters, and the thermodynamic properties of Na⁺, K⁺, Mg⁺⁺, Ca⁺⁺, and other aqueous species of geologic interest at temperatures to 900°C.  相似文献   

The solubilities of calcite,aragonite and vaterite in CO₂-H₂O solutions between 0 and 90°C,and an evaluation of the aqueous model for the system CaCO₃-CO₂-H₂O     

L.Niel Plummer  Eurybiades Busenberg 《Geochimica et cosmochimica acta》1982,46(6):1011-1040

Calculations based on approximately 350 new measurements (Ca_T-PCO₂) of the solubilities of calcite, aragonite and vaterite in CO₂-H₂O solutions between 0 and 90°C indicate the following values for the log of the equilibrium constants K_C, K_A, and K_V respectively, for the reaction CaCO₃(s) = Ca²⁺ + CO^2?₃: $\text{Log K}{}_{\mathrm{C}}\text{= ?171.9065 ? 0.077993T +}\text{2839.319}\text{T}\text{+ 71.595 log T}$$\text{Log K}{}_{\mathrm{A}}\text{= ?171.9773 ? 0.077993T +}\text{2903.293}\text{T}\text{+71.595 log T}$$\text{Log K}{}_{\mathrm{V}}\text{= ?172.1295 ? 0.077993T +}\text{3074.688}\text{T}\text{+ 71.595 log T}$ where T is in ^oK. At 25°C the logarithms of the equilibrium constants are ?8.480 ± 0.020, ?8.336 ± 0.020 and ?7.913 ± 0.020 for calcite, aragonite and vaterite, respectively.The equilibrium constants are internally consistent with an aqueous model that includes the CaHCO⁺₃ and CaCO⁰₃ ion pairs, revised analytical expressions for CO₂-H₂O equilibria, and extended Debye-Hückel individual ion activity coefficients. Using this aqueous model, the equilibrium constant of aragonite shows no PCO₂-dependence if the CaHCO⁺₃ association constant is between 0 and 90°C, corresponding to the value logK_Cahco⁺3 = 1.11 ± 0.07 at 25°C. The CaCO⁰₃ association constant was measured potentiometrically to be between 5 and 80°C, yielding logK_CaCO⁰3 = 3.22 ± 0.14 at 25°C.The CO₂-H₂O equilibria have been critically evaluated and new empirical expressions for the temperature dependence of K_H, K₁ and K₂ are $\text{log K}{}_{\mathrm{H}}\text{= 108.3865 + 0.01985076T ?}\text{6919.53}\text{T}\text{? 40.45154 log T +}\text{669365.}\text{T}{}^2$, $\text{log K}{}_1\text{= ?356.3094 ? 0.06091964T +}\text{21834.37}\text{T}\text{+ 126.8339 log T —}\text{1684915.}\text{T}{}^2$ and logK₂ = ?107.8871 ? 0.03252849T + 5151.79/T + 38.92561 logT ? 563713.9/T² which may be used to at least 250°C. These expressions hold for 1 atm. total pressure between 0 and 100°C and follow the vapor pressure curve of water at higher temperatures.Extensive measurements of the pH of Ca-HCO₃ solutions at 25°C and 0.956 atm PCO₂ using different compositions of the reference electrode filling solution show that measured differences in pH are closely approximated by differences in liquid-junction potential as calculated by the Henderson equation. Liquid-junction corrected pH measurements agree with the calculated pH within 0.003-0.011 pH.Earlier arguments suggesting that the CaHCO⁺₃ ion pair should not be included in the CaCO₃-CO₂-H₂O aqueous model were based on less accurate calcite solubility data. The CaHCO⁺₃ ion pair must be included in the aqueous model to account for the observed PCO₂-dependence of aragonite solubility between 317 ppm CO₂ and 100% CO₂.Previous literature on the solubility of CaCO₃ polymorphs have been critically evaluated using the aqueous model and the results are compared.  相似文献   

Tveitite,a new calcium yttrium fluoride     

Sveinung Bergstøl  Brenda B. Jensen  Henrich Neumann 《Lithos》1977,10(1):81-87

Tveitite is a new mineral with formula of the type $\text{Ca}{}_{\mathrm{1?x}}\text{(}\text{Y, RE}\text{)}{}_{\mathrm{x}}\text{F}{}_{\mathrm{2+x}}\text{where}\text{x}$ is approximately 0.3. It is found in a cleavelandite pegmatite at Høydalen in Tørdal, Telemark, S. Norway. The sub-cell is thought to be monoclinic, $\text{a}\text{′=3.924,}\text{b}\text{′=3.893,}\text{c}\text{′=5.525, ß=90°26′,}\text{Z}\text{=2}$. The structure is very similar to that of fluorite and can be described in terms of a pseudo-cubic cell $\text{[1}\text{1}\text{0]}{}_0\text{= 5.527, [110]}{}_0\text{= 5.527,}\text{c}\text{= 5.525, α = 90°18′, γ = 89°37′}$ which contains approximately 1[YCa₃F₉]. The mineral shows twinning in at lest three different directions giving a grating structure probably due to high-low inversion. DTA studies show an inversion point at about 670°C. Material heated above this temperature gives X-ray diffraction patterns corresponding to yttrofluorite (a₀ 5.528). The effect of trivalent ions on the stability of fluorite is discussed.  相似文献   

The significance of metamorphic fluorite in the Adirondacks     

S.R. Bohlen  E.J. Essene 《Geochimica et cosmochimica acta》1978,42(11):1669-1678

Thermodynamic calculations for selected silicate-oxide-fluorite assemblages indicate that several commonly occurring fluorite-bearing assemblages are restricted to relatively narrow fields at constant P?T. The presence of fayalite-ferrohedenbergite-fluorite-quartz ± magnetite and ferrosalite-fluorite-quartz-magnetite assemblages in orthogneisses from Au Sable Forks, Wanakena and Lake Pleasant, New York, buffered fluorine and oxygen fugacities during the granulite facies metamorphism in the Adirondack Highlands. These buffering assemblages restrict$\text{?}{}_{\mathrm{F}}{}_2$ to 10^{?29 ± 1} bar and $\text{?}{}_0{}_2$ to 10^{?16 ± 1} bar at the estimated metamorphic temperature of 1000K and pressure of 7 kbar. The assemblage biotite-magnetite-ilmenite-K-feldspar, found in the same Au Sable Forks outcrop as the fayalite-fluorite-ferrohedenbergite-quartz-magnetitie assemblage, restricts H₂O fugacities to less than 10^3·3 bar. These fugacities limit H₂ and HF fugacities to less than 10¹ bar for the Au Sable outcrop. The data indicate that relative to H₂O, O₂, H₂, F₂ and HF are not major species in the fluid equilibrated with Adirondack orthogneisses. The calculated F₂ fugacilies are similar to the upper limits possible for plagioclase-bearing rocks and probably represent the upper $\text{?}{}_{\mathrm{F}}{}_2$ limit for metamorphism in the Adirondacks and in other granulite facies terranes.  相似文献   

Theoretical prediction of phase relations among aqueous solutions and minerals: Salton Sea geothermal system     

Dennis K. Bird  Denis L. Norton 《Geochimica et cosmochimica acta》1981,45(9):1479-1494

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Rutile solubility and titanium coordination in silicate melts     

James E Dickinson  Paul C Hess 《Geochimica et cosmochimica acta》1985,49(11):2289-2296

The solubility of rutile has been determined in a series of compositions in the K₂O-Al₂O₃-SiO₂ system ($\text{K}{}^1\text{=}\text{K}{}_2\text{O}\text{(K}{}_2\text{O}$ + Al₂O₃) = 0.38–0.90), and the CaO-Al₂O₃-SiO₂ system ($\text{C}{}^1\text{=}\text{CaO}\text{(CaO + Al}{}_2\text{O}{}_3\text{)}\text{= 0.47–0.59}$). Isothermal results in the KAS system at 1325°C, 1400°C, and 1475°C show rutile solubility to be a strong function of the $\text{K}{}^1$ ratio. For example, at 1475°C the amount of TiO₂ required for rutile saturation varies from 9.5 wt% ($\text{K}{}^1\text{= 0.38}$) to 11.5 wt% ($\text{K}{}^1\text{= 0.48}$) to 41.2 wt% ($\text{K}{}^1\text{= 0.90}$). In the CAS system at 1475°C, rutile solubility is not a strong function of $\text{C}{}^1$. The amount of TiO₂ required for saturation varies from 14 wt% ($\text{C}{}^1\text{= 0.48}$) to 16.2 wt% ($\text{C}{}^1\text{= 0.59}$).The solubility changes in KAS melts are interpreted to be due to the formation of strong complexes between Ti and K⁺ in excess of that needed to charge balance Al³⁺. The suggested stoichiometry of this complex is K₂Ti₂O₅ or K₂Ti₃O₇. In CAS melts, the data suggest that Ca²⁺ in excess of A1³⁺ is not as effective at complexing with Ti as is K⁺. The greater solubility of rutile in CAS melts when $\text{C}{}^1$ is less than 0.54 compared to KAS melts of equal $\text{K}{}^1$ ratio results primarily from competition between Ti and Al for complexing cations (Ca vs. K).TiK_β x-ray emission spectra of KAS glasses ($\text{K}{}^1\text{= 0.43–0.60}$) with 7 mole% added TiO₂, rutile, and Ba₂TiO₄, demonstrate that the average Ti-O bond length in these glasses is equal to that of rutile rather than Ba₂TiO₄, implying that Ti in these compositions is 6-fold rather than 4-fold coordinated. Re-examination of published spectroscopic data in light of these results and the solubility data, suggests that the 6-fold coordination polyhedron of Ti is highly distorted, with at least one Ti-O bond grossly undersatisfied in terms of Pauling's rules.  相似文献   

Speciation of boron with Cu2+, Zn2+, Cd2+ and Pb2+ in 0.7 M KNO3 and in sea-water     

Constant M.G. van den Berg 《Geochimica et cosmochimica acta》1984,48(12):2613-2617

The stability constants, $\text{K}{}^1{}_{\mathrm{MB}}$, for borate complexes with the ions of Cu, Pb, Cd and Zn are determined in this work by DPASV in 0.7 M KNO₃ at metal concentrations of 10^?7 M. The acidity constants of the Cu²⁺ ion are determined by DPASV in the same conditions. The following values for log $\text{K}{}^1{}_{\mathrm{MB}}$ () have been obtained: CuB: 3.48, CuB₂: 6.13, PbB: 2.20, PbB₂: 4.41, ZnB: 0.9, ZnB₂: 3.32, CdB: 1.42, and CdB₂: 2.7, while the values for the acidity constants of Cu are $\text{pK}{}^1{}_{\mathrm{CuOH}}\text{= 7.66}$ and . At the low concentration of boron in 35%. S sea-water complexes with borate represent only about 0.2% Cu, 0.03% Pb, 0.02% Zn and 0.003% Cd.  相似文献   

Use of Pitzer's equations to determine the media effect on the formation of lead chloro complexes     

Frank.J. Millero  Robert H. Byrne 《Geochimica et cosmochimica acta》1984,48(5):1145-1150

The spectrophotometric measurements of chloro complexes of lead in aqueous HCl, NaCl, MgCl₂ and CaCl₂ solutions at 25°C have been analyzed using Pitzer's specific interaction equations. Parameters for activity coefficients of the complexes PbCl⁺, PbCl₂⁰ and PbCl₃^? have been determined for the various media. Values of $\text{K}{}_1\text{= 30.0 ± 0.6}$, $\text{K}{}_2\text{= 106.7 ± 2.1}$ and $\text{K}{}_3\text{= 73.0 ± 1.5}$ were obtained for the cumulative formation constants. [$\text{Pb}{}^{\mathrm{2+}}\text{+ nCl}{}^{\mathrm{?}}\text{→ PbCl}{}_{\mathrm{n}}{}^{\mathrm{2?n}}\text{)}$]. These values are in reasonable agreement with literature data. The Pitzer parameters for the PbCl ion pairs in various media were used to calculate the speciation of Pb²⁺ in an artificial seawater solution.  相似文献   

The effect of pressure on the solubility of minerals in water and seawater     

Frank J Millero 《Geochimica et cosmochimica acta》1982,46(1):11-22

The effect of presure on the solubility of minerals in water and seawater can be estimated from In where the volume (ΔV) and compressibility (ΔK) changes at atmospheric pressure (P = 0) are given by Values of the partial molal volume ($\text{V}\text{?}$) and compressibilty ($\text{K}\text{?}$) in water and seawater have been tabulated for some ions from 0 to 50°C. The compressibility change is quite large (~10 × 10^?3 cm³ bar^?1 mol^?1) for the solubility of most minerals. This large compressibility change accounts for the large differences observed between values of ΔV obtained from linear plots of In K_sp versus P and molal volume data (Macdonald and North, 1974; North, 1974). Calculated values of $\text{K}{}^{\mathrm{P}}{}_{\mathrm{sp}}\text{K}{}^{\mathrm{o}}{}_{\mathrm{sp}}$ for the solubility of CaCO₃, SrSO₄ and CaF₂ in water were found to be in good agreement with direct measurements (Macdonald and North, 1974). Similar calculations for the solubility of minerals in seawater are also in good agreement with direct measurements (Ingle, 1975) providing that the surface of the solid phase is not appreciably altered.  相似文献   

The solubility of noble gases in water and in NaCl brine     

S.P. Smith  B.M. Kennedy 《Geochimica et cosmochimica acta》1983,47(3):503-515

A direct-sampling, mass-spectrometric technique has been used to measure simultaneously the solubilities of He, Ne, Ar, Kr, and Xe in fresh water and NaCl brine (0 to 5.2 molar) from 0° to 65 °C, and at 1 atm total pressure of moist air. The argon solubility in the most concentrated brines is 4 to 7 times less than in fresh water at 65 °C and 0°C, respectively. The salt effect is parameterized using the Setschenow equation. where M is NaCl moiarity, βⁱ_o(T) and βⁱ(T) the Bunsen solubility coefficients for gas i in fresh water and brine, and Kⁱ_M(T) the empirical salting coefficient. Values of Kⁱ_M(T) are calculated using volumetric concentration units for noble gas and NaCl content and are independent of NaCl molarity. Below about 40°C, temperature coefficients of all Kⁱ_M are negative. The value of K^He_M is a minimum at 40°C. K^Ar_M decreases from about 0.40 at 0°C to 0.28 at 65 °C. The absolute magnitudes of the differences in salting coefficients (relative to K^Ar_M) decrease from 0° to 65°C. Over the range of conditions studied, all noble gases are salted out, and K^He_M ? K^Ne_M < K^Ar_M < K^Kr_M < K^Xe_M.From the solubility data, we calculated $\text{Δ}\text{G}{}^0{}_{\mathrm{tr}}$, $\text{Δ}\text{S}{}^0{}_{\mathrm{tr}}$, $\text{Δ}\text{H}{}^0{}_{\mathrm{tr}}$ and $\text{Δ}\text{C}{}^{\mathrm{O}}{}_{\mathrm{p,tr}}$ for the transfer of noble gases from fresh water to 1 molar NaCl solutions. At low temperatures $\text{Δ}\text{S}{}^0{}_{\mathrm{tr}}$, is positive, but decreases and becomes negative at temperatures ranging from about 25°C for He to 45°C for Xe. At low temperatures, the dissolved electrolyte apparently interferes with the formation of a cage of solvent molecules about the noble gas atom. At higher temperatures, the local environment of the gas atom in the brine appears to be slightly more ordered than in pure water, possibly reflecting the longer effective range of the ionic fields at higher temperature.The measured solubilities can be used to model noble gas partitioning in two-phase geothermal systems at low temperatures. The data can also be used to estimate the temperature and concentration dependence of the salt effect for other alkali halides. Extrapolation of the measured data is not possible due to the incompletely-characterized minima in the temperature dependence of the salting coefficients. The regularities in the data observed at low temperatures suggest relatively few high-temperature data will be required to model the behavior of noble gases in high-temperature geothermal brines.  相似文献   

Gibbsite solubility and thermodynamic properties of hydroxy-aluminum ions in aqueous solution at 25°C     

Howard M. May  Philip A. Helmke  Marion L. Jackson 《Geochimica et cosmochimica acta》1979,43(6):861-868

Solubility curves were determined for a synthetic gibbsite and a natural gibbsite (Minas Gerais, Brazil) from pH 4 to 9, in 0.2% gibbsite suspensions in 0.01 M NaNO₃ that were buffered by low concentrations of non-complexing buffer agents. Equilibrium solubility was approached from oversaturation (in suspensions spiked with Al(NO₃)₃ solution), and also from undersaturation in some synthetic gibbsite suspensions. Mononuclear Al ion concentrations and pH values were periodically determined. Within 1 month or less, data from over-and undersaturated suspensions of synthetic gibbsite converged to describe an equilibrium solubility curve. A downward shift of the solubility curve, beginning at pH 6.7, indicates that a phase more stable than gibbsite controls Al solubility in alkaline systems. Extrapolation of the initial portion of the high-pH side of the synthetic gibbsite solubility curve provides the first unified equilibrium experimental model of Al ion speciation in waters from pH 4 to 9.The significant mononuclear ion species at equilibrium with gibbsite are Al³⁺, AlOH²⁺, Al(OH)⁺₂ and Al(OH)^?₄, and their ion activity products are $\text{1K}{}_{50}\text{= 1.29 × 10}{}^8$, $\text{1K}{}_{\mathrm{s1}}\text{= 1.33 × 10}{}^3$, $\text{1K}{}_{\mathrm{s2}}\text{= 9.49 × 10}{}^{\mathrm{?3}}$ and $\text{1K}{}_{\mathrm{s4}}\text{= 8.94 × 10}{}^{\mathrm{?15}}$. The calculated standard Gibbs free energies of formation (ΔG°_f) for the synthetic gibbsite and the A1OH²⁺, Al(OH)⁺₂ and Al(OH)^?₄ ions are ?276.0, ?166.9, ?216.5 and ?313.5 kcal mol^?1, respectively. These ΔG°_f values are based on the recently revised ΔG°_f value for Al³⁺ (?117.0 ± 0.3 kcal mol_?1) and carry the same uncertainty. The ΔG°_f of the natural gibbsite is ?275.1 ± 0.4 kcal mol^?, which suggests that a range of ΔG°_f values can exist even for relatively simple natural minerals.  相似文献   

Revised values for the Gibbs free energy of formation of [Al(OH)_{4 aq}⁻], diaspore,boehmite and bayerite at 298.15 K and 1 bar,the thermodynamic properties of kaolinite to 800 K and 1 bar,and the heats of solution of several gibbsite samples     

Bruce S. Hemingway  Richard A. Robie  James A. Kittrick 《Geochimica et cosmochimica acta》1978,42(10):1533-1543

Solution calorimetric measurements compared with solubility determinations from the literature for the same samples of gibbsite have provided a direct thermochemical cycle through which the Gibbs free energy of formation of [Al(OH)_{4 aq}^?] can be determined. The Gibbs free energy of formation of [Al(OH)_{4 aq}^?] at 298.15 K is ?1305 ± 1 kJ/mol. These heat-of-solution results show no significant difference in the thermodynamic properties of gibbsite particles in the range from 50 to 0.05 μm.The Gibbs free energies of formation at 298.15 K and 1 bar pressure of diaspore, boehmite and bayerite are ?9210 ± 5.0, ?918.4 ± 2.1 and ?1153 ± 2 kJ/mol based upon the Gibbs free energy of [A1(OH)_{4 aq}^?] calculated in this paper and the acceptance of ?1582.2 ± 1.3 and ?1154.9 ± 1.2 kJ/mol for the Gibbs free energy of formation of corundum and gibbsite, respectively.Values for the Gibbs free energy formation of [Al(OH)_{2 aq}⁺] and [AlO_{2 aq}^?] were also calculated as ?914.2 ± 2.1 and ?830.9 ± 2.1 kJ/mol, respectively. The use of [AlC_{2 aq}^?] as a chemical species is discouraged.A revised Gibbs free energy of formation for [H₄SiO_4aq⁰] was recalculated from calorimetric data yielding a value of ?1307.5 ± 1.7 kJ/mol which is in good agreement with the results obtained from several solubility studies.Smoothed values for the thermodynamic functions C_P⁰, ($\text{H}{}_{\mathrm{T}}{}^0\text{- H}{}_{298}{}^0\text{)}\text{T}$, $\text{(}\text{G}{}_{\mathrm{T}}{}^0\text{- H}{}_{298}{}^0\text{)}\text{T}$, S_T⁰ - S₀⁰, $\text{ΔH}{}_{\mathrm{?,298}}{}^0$ kaolinite are listed at integral temperatures between 298.15 and 800 K. The heat capacity of kaolinite at temperatures between 250 and 800 K may be calculated from the following equation: C_P⁰ = 1430.26 ? 0.78850 T + 3.0340 × 10^?4T² ?1.85158 × 10^?4T²$\text{1}\text{2}\text{+ 8.3341 × 10}{}^6\text{T}{}^{\mathrm{?2}}$.The thermodynamic properties of most of the geologically important Al-bearing phases have been referenced to the same reference state for Al, namely gibbsite.  相似文献